Fine zeolite particle

ABSTRACT

A fine A-type zeolite particle having an average primary particle size of 0.1 μm or less and a variation coefficient of 90% or less, wherein a ratio of a peak area above a background level to all peak are in the range of 2θ=20° to 40° in a powder X-ray diffraction spectrum of said fine A-type zeolite particle is 30% or more; a process for preparing the fine A-type zeolite particle, comprising reacting a silica source with an aluminum source in the presence of an organic compound having an oxygen-containing functional group and a molecular weight of 100 or more; and a detergent composition comprising a surfactant and the fine A-type zeolite particle. The fine zeolite particle is suitably used for detergent builders, water treatment agent, fillers for paper, resin fillers, oxygen-nitrogen separating agents, adsorbents, catalyst carriers, soil improvers for gardening, polishing agents, and the like.

TECHNICAL FIELD

[0001] The present invention relates to a fine zeolite particle, aprocess for preparing the same, and a detergent composition comprisingthe fine zeolite particle.

BACKGROUND ART

[0002] Zeolites are crystalline aluminosilicates, which can beclassified into various crystal structures such as A-type, X-type andY-type by the arrangements of SiO₄ tetrahedrons and AlO₄ tetrahedrons.The zeolites have an even pore size depending upon the crystalstructures, thereby exhibiting a molecular sieve function. For thereason, the zeolites have been used for adsorbents, catalysts (carriers)and the like. In addition, since the zeolites have cationic exchangeabilities, they have been utilized as detergent builders, agents forwaste water treatment, and the like.

[0003] The functions of the zeolites greatly depend on the crystalstructure and the composition of the zeolite. For instance, the smallerthe Si/Al molar ratio of the zeolite, the larger the cationic exchangecapacity, and theoretically an A-type zeolite of which Si/Al is 1 ismost excellent. Therefore, the A-type zeolites having a high cationicexchange theoretical capacity have been mainly used as detergentbuilders.

[0004] Further, as detergent builders, there are especially neededzeolites excellent in not only the calcium ion exchange capacity butalso the calcium ion exchange rate. This is because when calcium ions inwater especially at an initial stage of washing can be captured in largeamounts, the detergency performance is improved. Since the calcium ionexchange rate of the zeolite is determined by a collision probability ofthe calcium exchange site of the zeolite with the calcium ions in water,the smaller the primary particle size of the zeolite, the higher thecalcium ion exchange rate of the zeolite.

[0005] In view of above, various proposals for preparing A-type zeoliteshaving a very small primary particle size have been so far made. Forinstance, Japanese Patent Laid-Open No. Sho 54-81200 discloses a processfor preparing a fine A-type zeolite particle comprising carrying out thereaction in the co-existence of an organic acid such as formic acid oracetic acid in a reaction mixture. However, in this process, theresulting zeolite particle only has a primary particle size of at least0.5 μm. On the other hand, Japanese Patent Laid-Open No. Hei 1-153514discloses a process for preparing a fine A-type zeolite particle havinga maximal particle size of 0.4 μm or less, comprising forming a zeolitenucleus at a temperature of 40° C. or less. However, even in thisprocess, the formed A-type zeolite particle has a primary particle sizeof at least 0.2 μm.

[0006] Meanwhile, a largest defect of the zeolite builder is in thatzeolite makes water turbid due to its water insolubility. In view ofthis problem, there has been proposed to reduce turbidity of the zeoliteby making an aggregate particle size of the zeolite small to a size ofequal to or less than a wavelength of visible light (0.4 μm) [Okumura,Nendo Kagaku 27, 21 (1987)]. In other words, the turbidity of thewashing water is reduced with making the aggregate particle sizesmaller, and when the aggregate particle size is 0.4 μm or less, thewashing water (zeolite concentration: 0.013% by weight) becomes almosttransparent. However, when the A-type zeolite of which aggregateparticle size is made very fine to the order of submicron size is madeinto a powdery state, the powder then re-aggregates to undesirably forma large aggregate. Also, it is very difficult to carry out solid-liquidseparation for the zeolite by means of filtration or concentration.Therefore, the zeolite has been actually fed to the detergent rawmaterial in a slurry state. At this time, the existence of Al ions inthe slurry (unreacted compounds of the zeolite raw materials orzeolite-eluted products) could be a factor of lowering the detergencyperformance. Therefore, the Al ion concentration in the slurry must becontrolled to a low level.

[0007] Generally, the aggregate particle size of A-type zeolite is madesmaller by means of vigorous stirring, pulverization or the like. Forinstance, as disclosed in Japanese Patent Laid-Open No. Hei 9-67117, anaggregate particle size and a primary particle size are made smaller tothe order of submicron size by mechanical pulverization. However, whenan A-type zeolite having a large primary particle size is subjected topulverization treatment, the cationic exchange abilities, i.e. thecationic exchange capacity and the cationic exchange rate, areundesirably lowered due to the crystallinity degradation caused by thedisintegration of primary crystals of the A-type zeolite and thedeterioration of the primary particle size distribution. In addition, ina water-based liquid of the zeolite after the pulverization treatment,ions of zeolite-constituting elements, i.e. Al, Si, and Na, especiallyAl, tend to be easily eluted in water, by the mechanochemical reactionof the zeolite particle surface. Therefore, when the zeolite is used fora detergent composition, there also arises a problem that the detergencyperformance of the composition is lowered.

[0008] In order to suppress the generation of the problems due to theprocess of making the aggregate particle size of the zeolite smaller,the disintegration of the zeolite primary crystals by the process ofmaking the size fine must be avoided. In order to avoid thedisintegration, it is desired that the primary particle size of A-typezeolite before pulverization is equal to or less than the aggregateparticle size of the zeolite after pulverization. Concretely, when theaverage aggregate particle size is made smaller to a size of 0.4 μm orless, the average primary particle size is generally 0.1 μm or less. Onthe basis of this fact, it is considered to be desirable that theaverage primary particle size of A-type zeolite before pulverization is0.1 μm or less in order to suppress the generation of the problemsmentioned above and to make the zeolite particle smaller by pulverizingthe particle until the particle has an average aggregate particle size(0.4 μm or less) which gives almost transparent washing water (zeoliteconcentration: 0.013% by weight). In addition, as long as a zeolite hasthe average primary particle size mentioned above, a desired averageaggregate particle size could be obtained without subjecting the zeoliteto pulverization treatment. However, as mentioned above, there are noexamples of a process for preparing a fine A-type zeolite particlehaving an average primary particle size of 0.1 μm or less withoutcarrying out pulverization treatment or the like after the reaction forpreparing the zeolite.

[0009] Ail object of the present invention is to provide a fine A-typezeolite particle having an average primary particle size of 0.1 μm orless and a variation coefficient of 90% or less, and excellent in thecationic exchange capacity, and giving small amounts of Al eluted inwater and little water turbidity in a water-based liquid, a process forpreparing the fine A-type zeolite particle, and a detergent compositioncomprising the fine A-type zeolite particle (hereinafter simply referredto as “fine zeolite particle or fine zeolite particles”), which is veryexcellent in the detergency and the rinsing performance.

[0010] These and other objects of the present invention will be apparentfrom the following description.

DISCLOSURE OF INVENTION

[0011] According to the present invention, there is provided:

[0012] (1) A fine A-type zeolite particle having an average primaryparticle size of 0.1 μm or less and a variation coefficient of 90% orless, wherein a ratio of a peak area above a background level to allpeak area in the range of 2θ=20° to 40° in a powder X-ray diffractionspectrum of said fine A-type zeolite particle is 30% or more;

[0013] (2) a process for preparing the fine A-type zeolite particle ofitem (1) above, comprising reacting a silica source with an aluminumsource in the presence of an organic compound having anoxygen-containing functional group and a molecular weight of 100 ormore; and

[0014] (3) a detergent composition comprising a surfactant and the fineA-type zeolite particle of item (1) above.

BEST MODE FOR CARRYING OUT THE INVENTION

[0015] The fine zeolite particle of the present invention can beprepared by reacting a silica source with an aluminum source in thepresence of an organic compound having an oxygen-containing functionalgroup and a molecular weight of 100 or more. By carrying out thereaction for preparing the zeolite as described above, the crystalgrowth of the zeolite can be suppressed, whereby a fine A-type zeoliteparticle having an average primary particle size of 0.1 μm or less canbe formed. In the fine zeolite particle obtained as described above,even if the particle were desirably further made smaller by mechanicalpulverization or the like until the particle has an average aggregateparticle size of 0.4 μm or less which gives substantially transparentwashing water (zeolite concentration: 0.013% by weight), thecrystallinity degradation, the deterioration of the average primaryparticle size distribution and the elution of Al (Al ion) can besuppressed.

[0016] Specifically, the fine zeolite particle of the present inventionis an A-type zeolite having an average primary particle size of 0.1 μmor less and a variation coefficient of 90% or less. The zeolite isexcellent in the cationic excellent abilities, and gives substantiallyno elution of Al ions into water from the zeolite in a water-basedliquid containing the zeolite and little water turbidity of the liquid.

[0017] The term “water-based liquid” as referred to herein is a liquidcomprising certain components and water as a medium including an aqueoussolution, a suspension, a dispersion or the like.

[0018] The fine zeolite particle of the present invention has an averageprimary particle size of 0.1 μm or less, preferably 0.08 μm or less,more preferably 0.05 μm or less. As mentioned above, when the averageaggregate particle size is made smaller by pulverization from theviewpoint of improving the turbidity of washing water, there arise someproblems such as crystallinity degradation of the zeolite. The extent ofgeneration of the problems depends on the average primary particle sizeof zeolite before pulverization: The larger the average primary particlesize, the more serious the problem. Generally, in a A-type zeolitehaving an average primary particle size larger than 0.1 μm, the primarycrystal itself is disintegrated by pulverization, so that the ions ofconstituent elements are eluted from the zeolite in large amounts andthe crystallinity degradation progresses drastically as mentioned above.Since the fine zeolite particle of the present invention has an averageprimary particle size within the above-mentioned range, the generationof the problems caused by pulverization would be substantiallycompletely suppressed. The average primary particle size can bedetermined by the method described in Examples set forth below.

[0019] The particle size distribution of the zeolite having the averageprimary particle size in the range mentioned above can be evaluated byvariation coefficient The variation coefficient can be calculatedaccording to the method described in Examples set forth below. Theparticle size distribution of the fine zeolite particle of the presentinvention is highly uniform satisfying the variation coefficient of theabove-mentioned average primary particle size of 90% or less, preferably70% or less, more preferably 50% or less, still more preferably 35% orless. In other words, the fine zeolite particle of the present inventionis composed of a zeolite having a desired average primary particle sizeof 0.1 μm or less and a uniform particle size distribution, whichcontributes to the exhibition of excellent cationic exchange abilities.In an A-type zeolite having a large average primary particle size of 1μm or more, the state of disintegration of the primary crystals causedby pulverization can be captured by scanning electron microscope, andthe variation coefficient of the average primary particle size becomesgenerally large by the pulverization. On the other hand, in the finezeolite particle of the present invention, the disintegration of theprimary crystals caused by pulverization is substantially completelysuppressed, and an aggregate of the primary particles is merelydisaggregated during the pulverization. Therefore, the changes in thevariation coefficient caused by pulverization do not substantially takeplace.

[0020] The fine zeolite particle of the present invention is an A-typezeolite, which can show substantially the same powder X-ray diffractionpattern as that of a known A-type zeolite (Joint Committee on PowderDiffraction Standards No. 38-241). Here, as long as the powder X-raydiffraction pattern of the fine zeolite particle is substantially thesame as that of a known one, the pattern may contain peaks ascribed toother crystalline substances and halo peaks belonging to amorphoussubstances. In addition, a ratio (powder X-ray diffraction intensityratio) of a powder X-ray diffraction peak intensity I₄₁₀ of the finezeolite particle of the present invention to an I₄₁₀ of d=0.3 nmbelonging to a plane (410) of a commercially available A-type zeolite(for instance, “TOYOBUILDER” manufactured by Tosoh Corporation) havingan average primary particle size of 1 μm or more is preferably 10% ormore, more preferably 20% or more, from the viewpoint of improving thecationic exchange abilities.

[0021] In addition, the crystallinity of the fine zeolite particle ofthe present invention can be evaluated by a ratio (A_(r)) of a peak areaabove the background level in all peak area in the range of 2θ=20° to40° in the powder X-ray diffraction spectrum. The A_(r) can beconcretely calculated by the method described in Examples set forthbelow. The fine zeolite particle of the present invention has A_(r) of30% or more, preferably 33% or more, within which range the proportionof amorphous portions in the primary crystal structure is small,excellent cationic exchange abilities can be exhibited, and the loweringof the detergency performance due to elution of Al ions can besuppressed.

[0022] On the other hand, since the A_(r) shows the crystallinity of thezeolite, an extent of the crystallinity degradation caused bypulverization can be evaluated as a crystallinity degradation ratio onthe basis of A_(r) obtained before and after the pulverization. Thecrystallinity degradation ratio can be calculated by the methoddescribed in Examples set forth below. In the fine zeolite particle ofthe present invention, the crystallinity degradation ratio is preferably50% or less, more preferably 40% or less, still more preferably 35% orless, from the viewpoints of keeping primary crystallinity, therebysuppressing the lowering of cationic exchange abilities and the elutionof Al ions.

[0023] The fine zeolite particle of the present invention has an averageaggregate particle size of preferably 0.4 μm or less, more preferably0.3 μm or less. The average aggregate particle size can be determined bythe method described in Examples set forth below. The degree ofturbidity by the fine zeolite particle of the present invention can bealso determined as turbidity by the method described in Examples setforth below. When the average aggregate particle size is within therange mentioned above, the turbidity can be preferably 30% or less, morepreferably 20% or less. When the average aggregate particle size and theturbidity are within the above ranges, in the case, for instance, wherethe zeolite is added to a detergent composition such as a laundrypowdery detergent and a laundry liquid detergent, it is preferablebecause the water turbidity of washing water and initial rinsing wateris remarkably improved so that the water becomes substantiallytransparent, and a problem that the zeolite remains on a fiber surfacedoes not also take place.

[0024] When the fine zeolite particle does not have an average aggregateparticle size of 0.4 μm or less as a primary product obtained by theprocess for preparing the fine zeolite particle of the present inventiondescribed below, the fine zeolite particle may be further subjected topulverization as described below as desired. As described above, sincethe fine zeolite particle of the present invention has an averageprimary particle size of 0.1 μm or less, the lowering of primarycrystallinity is small even if subjected to appropriate pulverization togive an average aggregate particle size of 0.4 μm or less. Therefore,substantially no problems on the lowering of cationic exchange abilitiesand on the elution of Al in large amounts take place. In the presentinvention, it is preferable that the fine zeolite particle obtained as aprimary product is appropriately pulverized, from the viewpoint offurther improving the transparency of washing water, when the finezeolite particle of the present invention is used as a detergentbuilder.

[0025] In addition, when the water-based liquid of the fine zeoliteparticle of the present invention is prepared, the ratio of the amountof Al eluted in water is preferably less than 4% by weight, morepreferably 3.5% by weight or less, still more preferably 3.2% by weightor less, of the entire amount of Al contained in the fine zeoliteparticle. It is preferable that the proportion of the amount of Aleluted is within the range mentioned above, because in the case wherethe fine zeolite particle is added to, for instance, a detergentcomposition, the lowering of qualities (detergency performance, storagestability and the like) of the detergent composition can be suppressed.In addition, the lowering of primary crystallinity and the amount of Aleluted are small even if subjected to appropriate pulverization to givean average aggregate particle size within the desired range. Theproportion of the amount of Al eluted in water can be determined by themethod described in Examples set forth below.

[0026] Also, the fine zeolite particle of the present invention isexcellent in the cationic exchange abilities. Here, the term “cationicexchange abilities” refer to both the cationic exchange rate and thecationic exchange capacity. More concretely, the term “cationic exchangerate” refers to an amount of Ca which is ion-exchanged per one gram of azeolite in one minute, and the term “cationic exchange capacity” refersto an amount of Ca which is ion-exchanged per one gram of a zeolite inten minutes. The cationic exchange rate and the cationic exchangecapacity can be determined by the methods described in Examples setforth below.

[0027] The above-mentioned cationic exchange rate (CER) is preferably180 mg CaCO₃/g or more, more preferably 200 mg CaCO₃/g or more, stillmore preferably 220 mg CaCO₃/g or more. On the other hand, theabove-mentioned cationic exchange capacity (CEC) is preferably 200 mgCaCO₃/g or more, more preferably 210 mg CaCO₃/g or more, still morepreferably 220 mg CaCO₃/g or more. It is preferable that the cationicexchange abilities of the fine zeolite particle of the present inventionare within the above ranges, because in a case where the zeolite is usedfor a detergent composition, the detergency performance of thecomposition is remarkably improved. In addition, there are littlecrystallinity degradation and deterioration of particle sizedistribution even if subjected to appropriate pulverization to give anaverage aggregate particle size within the desired range. Therefore,there are substantially no changes in the cationic exchange abilities.

[0028] The fine zeolite particle of the present invention has acomposition, in the anhydride form, represented by the general formulaxM₂OySiO₂Al₂O₃zMeO, wherein M is an alkali metal atom, Me is analkaline earth atom. In the formula, it is preferable that x is from 0.2to 4, y is from 0.5 to 6, and z is from 0 to 0.2, and it is morepreferable that x is from 0.8 to 2, y is from 1 to 3, and z is from0.001 to 0.1. Those elements other than the elements given in the abovecompositional formula can be contained in the composition within therange so as not to lower the cationic exchange abilities. Theabove-mentioned alkali metal atom refers to those elements belonging toGroup IA of the Periodic Table, and is not particularly limited. Amongthe alkali metal atoms, sodium is preferable. The fine zeolite particleof the present invention can contain two or more alkali metal atoms. Inaddition, the above-mentioned alkaline earth metal atom refers to thoseelements belonging to Group IIA of the Periodic Table, and is notparticularly limited. Among the alkaline earth metal atoms, calcium andmagnesium are preferable. The fine zeolite particle of the presentinvention can contain two or more alkaline earth metal atoms.

[0029] Next, the process for preparing a fine zeolite particle of thepresent invention will be described. One of the greatest features of theprocess resides in that a silica source is reacted with an aluminumsource in the presence of an organic compound having anoxygen-containing functional group and a molecular weight of 100 or more(hereinafter referred to as “crystallization inhibitor”). Since thereaction is carried out in the presence of the crystallizationinhibitor, the flowability of the reaction mixture (slurry) comprising asilica source and an aluminum source is increased, thereby improving thereaction efficiency. At the same time, the crystal growth of the zeoliteis suppressed, so that the zeolite particle having small average primaryparticle size and even particle size distribution can be formed.

[0030] The mechanism for suppression of the zeolite crystal growth bythe coexistence of the above-mentioned crystallization inhibitor ispresumably as follows: Silanol (Si-OH) group or the like on the surfaceof a zeolite nucleus interacts with oxygen atom of the functional groupvia a hydrogen bonding-like interaction, so that the zeolite nucleussurface is stabilized, thereby suppressing the crystal growth (Ostwaldgrowth). Also, the zeolite nucleus themselves are sterically repulseddue to the steric hindrance of the crystallization inhibitors adsorbedto (interacting with) the zeolite nucleus, whereby the crystal growth bycollision of the zeolite nuclei themselves is inhibited. As a result, afine zeolite particle having a small average primary particle size isformed.

[0031] The silica source and the aluminum source which are used in theprocess for preparing a fine zeolite particle of the present inventionare not particularly limited. For instance, as the silica source, acommercially available water glass can be used, and silica rock, silicasand, cristobalite, kaolin, cullets, and the like can be also used.Further, they may be properly diluted with water or an aqueous alkalimetal hydroxide upon use. In addition, as the aluminum source,aluminum-containing compounds such as aluminum hydroxide, aluminumsulfate, and aluminum chloride can be used, and powder or a water-basedliquid of an alkali metal aluminate, especially sodium aluminate, ispreferably used. These compounds may be commercially available products.As the water-based liquid of sodium aluminate, those obtained bydissolving aluminum hydroxide and an alkali metal hydroxide in waterwith heating can be used.

[0032] The crystallization inhibitor has a molecular weight of 100 ormore, preferably 200 or more, more preferably 400 or more. When themolecular weight of the crystallization inhibitor is less than 100,there is little steric hindrance of the crystallization inhibitoradsorbed to (interacting with) the zeolite nucleus surface, so that theprogress of the crystal growth by collision of the zeolite nucleithemselves cannot be effectively suppressed, whereby a desiredcrystallization inhibiting effect cannot be obtained. In addition, themolecular weight of the crystallization inhibitor is preferably 60000 orless, more preferably 30000 or less, still more preferably 10000 orless, within which range the crystallization inhibitor is sufficientlydissolved in the reaction mixture comprising a silica source and analuminum source, so that the amount of the crystallization inhibitoradsorbed to the zeolite nucleus (amount of the crystallization inhibitorinteracting with the zeolite nucleus) is increased, whereby acrystallization inhibiting effect is sufficiently exhibited. Especially,the crystallization inhibitor has a molecular weight of preferably from100 to 60000, more preferably from 200 to 30000, still more preferablyfrom 400 to 10000. In the present invention, when the crystallizationinhibitor has one or more hydroxyl groups or one or more carboxyl groupsat one end or both ends, the molecular weight of the crystallizationinhibitor can be determined by quantitative analysis of functionalgroups, for instance, the analysis of hydroxyl value or acid value. Inaddition, for instance, when the molecular weight is 1000 or more, themolecular weight is a weight-average molecular weight, which can bedetermined by GPC (gel permeation chromatography) in accordance with aknown method.

[0033] The functional group of the crystallization inhibitor is notparticularly limited, as long as it contains oxygen atom. The preferableoxygen-containing functional group includes, for instance, OR group,COOR group, SO₃R group, PO₄R group, CO group, CONH group, and the like,among which OR group and/or COOR group is more preferable. R is at leastone member selected from a saturated or unsaturated organic group having1 to 22 carbon atoms, hydrogen atom and an alkali metal atom. Thesaturated or unsaturated organic group having 1 to 22 carbon atomsincludes, for instance, ethylene group, vinyl group, phenyl group, hexylgroup, dodecyl group, and the like. The alkali metal atom includes, forinstance, sodium, potassium, and the like. These functional groups mayconstruct a main chain, or they may construct a side chain. The numberof functional groups per one molecule of the crystallization inhibitoris not particularly limited. The number of functional groups per onemolecule is preferably 2 or more, more preferably 3 or more, still morepreferably 4 or more. It is preferable that the number of functionalgroups per one molecule is within the above range, from the viewpoint ofgiving a sufficient number of interaction site of the zeolite nucleusand the crystallization inhibitor, thereby giving an excellentcrystallization inhibiting effect of the zeolite. In addition, thenumber of functional groups per one molecule is preferably 1000 or less,more preferably 500 or less, still more preferably 200 or less. It ispreferable that the number of functional groups per one molecule iswithin the above range, from the viewpoints of giving appropriatemolecular weight of the crystallization inhibitor for sufficientlydissolving the compound in a reaction mixture, whereby exhibiting anexcellent crystallization inhibiting effect.

[0034] Concrete examples of the crystallization inhibitor includenonionic surfactants such as polyoxyethylene lauryl ether; andwater-soluble polymers such as polyethylene glycol, polyvinyl alcohols,acrylate-based polymers, carboxymethyl cellulose and hexametaphosphate;and the like, without being limited thereto. These compounds can be usedas a mixture of two or more kinds.

[0035] The feeding composition for preparing the fine zeolite particleof the present invention, as expressed by an SiO₂/Al₂O₃ molar ratio, ispreferably 0.5 or more, more preferably 1 or more, still more preferably1.5 or more. It is preferable that the SiO₂/Al₂O₃ molar ratio is withinthe above range, from the viewpoints of stabilizing the crystalstructure of the zeolite, thereby suppressing the lowering ofcrystallinity, and accelerating the progress of crystallization. Inaddition, the SiO₂/Al₂O₃ molar ratio is preferably 4 or less, morepreferably 3 or less, still more preferably 2.5 or less. It ispreferable that the SiO₂/Al₂O₃ molar ratio is within the above range,from the viewpoints of favorably progressing the reaction, therebygiving sufficient cationic exchange abilities.

[0036] Also, the feeding composition of the compound containing analkali metal, as expressed by an M₂O/Al₂O₃ molar ratio, the alkali metal(M) being shown as an oxide, is preferably 0.08 or more, more preferably0.8 or more, still more preferably 1.4 or more. It is preferable thatthe M₂O/Al₂O₃ molar ratio is within the above range, from the viewpointof accelerating the progress of crystallization. In addition, theM₂O/Al₂O₃ molar ratio is preferably 20 or less, more preferably 5 orless, still more preferably 3 or less. It is preferable that theM₂O/Al₂O₃ molar ratio is within the above range, from the viewpoint offavorable productivity.

[0037] Further, the feeding composition of the compound containing analkali metal and water in the reaction system, as expressed by anM₂O/H₂O molar ratio, is preferably 0.02 or more, more preferably 0.05 ormore, still more preferably 0.07 or more. It is preferable that theM₂O/H₂O molar ratio is within the above range, from the viewpoint ofgiving an appropriate crystallization rate, thereby favorablyprogressing the formation of the fine zeolite particle with smallaverage primary particle size. In addition, the M₂O/H₂O molar ratio ispreferably 0.2 or less, more preferably 0.15 or less, still morepreferably 0.1 or less. It is preferable that the M₂O/H₂O molar ratio iswithin the above range, from the viewpoint of properly progressing thereaction, thereby giving sufficient cationic exchange abilities.

[0038] Furthermore, the feeding composition of the compound containingan alkaline earth metal, as expressed by an MeO/Al₂O₃ molar ratio, thealkaline earth metal (Me) being shown as an oxide, is preferably 0 to0.1. The MeO/Al₂O₃ molar ratio is more preferably 0.005 or more, stillmore preferably 0.01 or more, from the viewpoints of accelerating makingthe average primary particle size fine and improving thermal stability.In addition, the MeO/Al₂O₃ molar ratio is preferably 0.1 or less, morepreferably 0.08 or less, still more preferably 0.05 or less, from theviewpoint of improving the ion exchange abilities.

[0039] Moreover, the feeding composition of the aluminum in the reactionsystem, as expressed by an Al₂O₃/H₂O molar ratio, is preferably 0.01 ormore, more preferably 0.02 or more, still more preferably 0.03 or more.It is preferable that the Al₂O₃/H₂O molar ratio is within the aboverange, from the viewpoints of excellent productivity and acceleration ofmaking the average primary particle size fine. In addition, theAl₂O₃/H₂O molar ratio is preferably 0.25 or less, more preferably 0.2 orless, still more preferably 0.1 or less. It is preferable that theAl₂O₃/H₂O molar ratio is within the above range, from the viewpoint ofgiving an excellent flowability to the slurry, thereby efficientlyprogressing the reaction.

[0040] When the solid content is defined as a total weight of eachinorganic element contained in the raw materials used constituting thefine zeolite particle of the present invention calculated as an oxide,and the concentration of the solid content during the reaction isdefined as the concentration of the solid content in the entirewater-containing slurry, the concentration of the solid content ispreferably 10% by weight or more, more preferably 20% by weight or more,still more preferably 30% by weight or more, from the viewpoint ofproductivity In addition, the concentration of the solid content ispreferably 70% by weight or less, more preferably 60% by weight or less,still more preferably 50% by weight or less, from the viewpoint of theflowability of the slurry.

[0041] On the other hand, the feeding amount of the above-mentionedcrystallization inhibitor is preferably 1% by weight or more, morepreferably 5% by weight or more, still more preferably 10% by weight ormore, in the reaction mixture comprising a silica source and an aluminumsource, from the viewpoint of exhibiting a crystallization inhibitingeffect. In addition, the feeding amount of the above-mentionedcrystallization inhibitor is preferably 80% by weight or less, morepreferably 60% by weight or less, still more preferably 50% by weight orless, from the viewpoint of productivity.

[0042] The fine zeolite particle of the present invention is, forinstance, prepared by feeding a silica source, an aluminum source and acrystallization inhibitor each in a separate vessel, and properly mixingthese components in accordance with a known method to react thecomponents. During the reaction, other components may be added withinthe range so as not to hinder the preparation of the fine zeoliteparticle of the present invention. Such other components include, forinstance, calcium chloride, magnesium chloride and the like. It ispreferable that each of the silica source, the aluminum source and thecrystallization inhibitor is fed to the reaction in the form ofwater-based liquid, from the viewpoint of homogeneously and efficientlycarrying out the reaction.

[0043] The mixing order of the silica source, the aluminum source andthe crystallization inhibitor is not particularly limited. A liquidmixture of the aluminum source and the crystallization inhibitor may bemixed with the silica source, or a liquid mixture of the silica sourceand the crystallization inhibitor may be mixed with the aluminum source.Alternatively, the silica source and the aluminum source may besimultaneously fed to the crystallization inhibitor, and mixed; or thecrystallization inhibitor may be previously mixed with the silica sourceand/or the aluminum source, and the silica source is then mixed with thealuminum source.

[0044] In addition, the mixing method is not particularly limited. Forinstance, the silica source, the aluminum source and the crystallizationinhibitor may be subjected to line-mixing, with circulating the silicasource, the aluminum source and the crystallization inhibitor togetherin a specified circulation line.

[0045] Alternatively, the silica source, the aluminum source and thecrystallization inhibitor may be mixed in a reaction vessel (batch-typemixing). The reaction time is not particularly limited because itdepends upon the reaction temperature. The reaction time is preferably30 seconds or more, more preferably 1 minute or more, still morepreferably 5 minutes or more, from the termination of adding all thefeeding components, from the viewpoint of the homogeneity of reaction.Also, the reaction time is preferably 120 minutes or less, morepreferably 60 minutes or less, still more preferably 30 minutes or less,from the viewpoint of productivity.

[0046] The reaction temperature is preferably 10° C. or more, morepreferably 20° C. or more, still more preferably 40° C. or more. It ispreferable that the reaction temperature is within the range specifiedabove, from the viewpoints of giving excellent flowability of thereaction mixture and carrying out homogeneous reaction. Also, thereaction temperature is preferably 100° C. or less, more preferably 90°C. or less, still more preferably 80° C. or less. It is preferable thatthe reaction temperature is within the range specified above, from theviewpoints of proper energy load and an economical advantage on anindustrial scale.

[0047] The crystallization can be carried out by aging the reactionmixture after the reaction at a temperature equal to or higher than thereaction temperature under stirring. The aging temperature is notparticularly limited. The aging temperature is preferably 50° C. ormore, more preferably 70° C. or more, still more preferably 80° C. ormore, from the viewpoint of the crystallization rate. In addition, theaging temperature is preferably 120° C. or less, more preferably 100° C.or less, still more preferably 90° C. or less, from the viewpoints ofenergy load and pressure resistance of the reaction vessel. Although theaging time depends upon the aging temperature, the aging time ispreferably 1 minute or more, more preferably 10 minutes or more, stillmore preferably 30 minutes or more, from the viewpoint of sufficientlycarrying out the crystallization. In addition, the aging time ispreferably 300 minutes or less, more preferably 180 minutes or less,still more preferably 120 minutes or less, from the viewpoints of thelowering of cationic exchange abilities caused by by-product reaction ofsodalite and the productivity.

[0048] After the termination of aging, the crystallization is terminatedby cooling, diluting or filtering and washing the slurry, orneutralizing the slurry by adding an acid. In the case of filtering andwashing the slurry, it is preferable that washing is carried out untilpH of the washing preferably becomes 12 or less. Also, in the case ofneutralizing the slurry, the acid used for the neutralization is notparticularly limited, and sulfuric acid, hydrochloric acid, nitric acid,carbon dioxide gas, oxalic acid, citric acid, tartaric acid, fumaricacid, succinic acid and the like can be used. Sulfuric acid and carbondioxide gas are preferable, from the viewpoints of preventing corrosionof the devices and lowering costs. It is preferable that the pH of theslurry is adjusted to 8 to 12. After the termination of thecrystallization, the fine zeolite particle of the present invention inthe form of slurry is obtained. Further, this slurry may beappropriately subjected to filtration or centrifugation to separatezeolite precipitates, and the precipitates are further washed and driedinto the form of cake or powder.

[0049] Next, the fine zeolite particle obtained as a primary product maybe pulverized as desired, from the viewpoint of adjusting the zeoliteparticle to show a desired average aggregate particle size. Thepulverization may be carried out by directly subjecting the slurry ofthe above-mentioned fine zeolite particle to wet pulverization, oralternatively re-dispersing the resulting fine zeolite particle in asolvent, and thereafter subjecting the dispersion to wet pulverization,or alternatively subjecting a powdery fine zeolite particle to drypulverization. Each of the pulverization methods can be carried out inaccordance with a known method.

[0050] For instance, when the fine zeolite particle of the presentinvention is added to the detergent composition of the present inventiondescribed below, the zeolite particle may be added in a slurry form. Inthis case, it is preferable to carry out wet pulverization, from theviewpoint of simplicity in the preparation steps. The pulverizationmethod employed herein is not particularly limited. For instance, theremay be employed pulverizers and the like described in Kagaku KogakukaiEdited, Kagaku Kogaku Binran (published by Maruzen Publishing, 1988),Fifth Edition, pages 826 to 838. Also, the dispersion medium to be usedfor wet pulverization includes water, alcohol solvents such as ethanol,surfactants such as polyoxyethylene alkyl ethers, polymer dispersants,and the like. They can be used alone or as a mixed solution of two ormore kinds. When the slurry is subjected to wet pulverization, thezeolite concentration in the slurry is preferably 5% by weight or more,more preferably 10% by weight or more, still more preferably 15% byweight or more, from the viewpoint of productivity. In addition, thezeolite concentration in the slurry is preferably 60% by weight or less,more preferably 55% by weight or less, still more preferably 50% byweight or less, from the viewpoint of the handleability of the zeoliteslurry during the wet pulverization and from the viewpoint of preventionof the re-aggregation of the fine zeolite particle after pulverization.

[0051] The fine zeolite particle of the present invention is suitablyused for, for instance, detergent builders, water treatment agents,fillers for paper, resin fillers, oxygen-nitrogen separating agents,adsorbents, catalyst carriers, soil improvers for gardening, polishingagents, and the like, and especially preferably used as detergentbuilders.

[0052] Further, the detergent composition of the present invention willbe described. The detergent composition comprises a surfactant and thefine zeolite particle of the present invention. Owing to the highcationic exchange abilities, the low Al ion-eluting property and furtherthe low turbidity of the zeolite, the detergent composition exhibitsexcellent detergency performance and makes rinsing water substantiallynot turbid, so that the amount of water and the time required forrinsing can be remarkably shortened.

[0053] The content of the fine zeolite particle in the detergentcomposition of the present invention is not particularly limited. Thecontent of the fine zeolite particle in the detergent composition ispreferably 1% by weight or more, more preferably 3% by weight or more,still more preferably 5% by weight or more, from the viewpoint ofexhibiting satisfactory detergency performance. In addition, the contentof the fine zeolite particle is preferably 60% by weight or less, morepreferably 50% by weight or less, still more preferably 40% by weight orless, from the viewpoint of stability in the production of the detergentcomposition. The content of the fine zeolite particle in the detergentcomposition is preferably from 1 to 60% by weight, more preferably from3 to 50% by weight, still more preferably from 5 to 40% by weight. Inaddition, in the detergent composition of the present invention, theremay be formulated other known zeolites together with the fine zeoliteparticle of the present invention. Such other zeolites may becommercially available zeolites, and the crystal structure of suchzeolites may be P-type, X-type and the like other than the A-type. Also,the zeolites may be a mixture of two or more of these zeolites. Theaverage primary particle size and the average aggregate particle size ofthe other zeolite are not particularly limited. The average primaryparticle size is preferably 10 μm or less, more preferably 5 μm or less,still more preferably 2 μm or less, from the viewpoint of the cationicexchange rate. Also, the average aggregate particle size is preferably15 μm or less, more preferably 10 μm or less, still more preferably 5 μmor less, from the viewpoint of the dispersibility in water. Theproportion of the fine zeolite particle of the present inventioncontained in all the zeolite used is preferably 10% by weight or more,more preferably 20% by weight or more, still more preferably 50% byweight or more, from the viewpoint of securing the exhibition of thedesired effect of the detergent composition of the present invention.

[0054] The surfactant to be added to the detergent composition of thepresent invention is not particularly limited. For instance, there canbe exemplified nonionic, anionic, cationic and amphoteric surfactants.

[0055] Concrete examples of the nonionic surfactants include those knownnonionic surfactants disclosed in “Chapter 3, Section 1 of ShuchiKanyoGijutsushu (Iryoyo Funmatsusenzai) [Known and Well Used TechnicalTerminologies (Laundry Powder Detergent)]” a publication made by theJapanese Patent Office. Other nonionic surfactants includepolyoxyethylene alkyl phenyl ethers, polyoxyethylene alkylamines,sucrose fatty acid esters, glycerol fatty acid monoesters, higher fattyacid alkanolamides, polyoxyethylene higher fatty acid alkanolamides,amine oxides, alkyl glycosides, alkyl glyceryl ethers, N-alkylgluconamides and the like.

[0056] Examples of the anionic surfactants include those known anionicsurfactants disclosed in “Chapter 3, Section 1 of ShuchiKanyoGijutsushu (Iryoyo Funmatsusenzai) [Known and Well Used TechnicalTerminologies (Laundry Powder Detergent)]” a publication made by theJapanese Patent Office. The counter ions for the anionic surfactant areselected from the group consisting of sodium ion, potassium ion,magnesium ion, calcium ion, a cation formed by protonating an amine suchas ethanolamines, a quaternary ammonium salt, and mixtures thereof.

[0057] Examples of the cationic surfactants include those known cationicsurfactants disclosed in “Chapter 3, Section 1 of ShuchiKanyoGijutsushu (Iryoyo Funmatsusenzai) [Known and Well Used TechnicalTerminologies (Laundry Powder Detergent)]” a publication made by theJapanese Patent Office.

[0058] Examples of the amphoteric surfactants include those knownamphoteric surfactants disclosed in “Chapter 3, Section 1 ofShuchiKanyo Gijutsushu (Iryoyo Funmatsusenzai) [Known and Well UsedTechnical Terminologies (Laundry Powder Detergent)]” a publication madeby the Japanese Patent Office.

[0059] The above-mentioned surfactants can be used alone or in admixtureof two or more kinds. In addition, the surfactants can be selected fromthose of the same or different kinds.

[0060] The content of the surfactant in the detergent composition of thepresent invention is not particularly limited. The content of thesurfactant in the detergent composition is preferably 1% by weight ormore, more preferably 5% by weight or more, still more preferably 10% byweight or more, from the viewpoint of detergency. Also, the content ofthe surfactant is preferably 90% by weight or less, more preferably 70%by weight or less, still more preferably 60% by weight or less, from theviewpoint of the productivity of the detergent composition. The contentof the surfactant in the detergent composition of the present inventionis preferably from 1 to 90% by weight, more preferably from 5 to 70% byweight, still more preferably from 10 to 60% by weight.

[0061] In the detergent composition of the present invention, besidesthe above-mentioned surfactant and the fine zeolite particle of thepresent invention, there can be properly added various additives whichare usually added to laundry detergents. The content of these additivescan be properly adjusted as long as they do not inhibit the desiredeffects of the detergent composition of the present invention.

[0062] The above-mentioned additives include, for instance, otherinorganic builders, organic builders, enzymes, re-depositionpreventives, fluorescers, viscosity-controlling agents, solvents,bleaching agents, dispersing agents, perfume, and the like. Theinorganic builder besides the zeolite includes silicates, carbonates,sulfates, sulfites, condensed phosphates, sodium chloride, and the like,and these salts are preferably formed with an alkali metal. The organicbuilder includes organic alkalizing agents such as alkanolamines such astriethanolamine, diethanolamine and monoethanolamine; organiccation-exchanging agents such as aminopolyacetates such asethylenediaminetetraacetate, oxycarboxylates such as citric acid,polycarboxylates such as polyacrylic acids and acrylic acid-maleic acidcopolymers, and the like, and these salts are preferably formed with analkali metal or ammonium. The enzyme includes cellulase, amylase,cannase, lipase, protease, and the like. The re-deposition agentincludes polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone,carboxymethyl cellulose, and the like. The viscosity-controlling agentand the solvent include lower alcohols such as isopropanol, glycols suchas ethylene glycol, glycerol, and the like. The bleaching agent includesinorganic peroxide bleaching agents such as sodium percarbonate andsodium perborate, or a mixture of these inorganic peroxide bleachingagents with a bleaching activator. Examples of the bleaching activatorinclude an organic compound having a reactive acyl group for forming anorganic peroxide. Concrete examples of the bleaching activator includesodium lauroyloxybenzenesulfonate, sodium decanoyloxybenzenesulfonate,lauroyloxybenzoic acid, decanoyloxybenzoic acid and the like. Besidesthem, bleaching activating catalysts such as manganese, cobalt and ironcomplexes can be added as a bleaching activator.

[0063] The detergent composition of the present invention can beobtained by mixing and stirring each of the components mentioned aboveaccording to a known method, and thereafter optionally subjecting theresulting mixture to such a treatment as granulation. Since thecomposition comprises the fine zeolite particle of the presentinvention, the composition is very excellent in the detergency and therinsing performance. The detergency and the rinsing performance can beevaluated by the methods described in Examples set forth below.

[0064] The determination values of the sample properties in Examples andComparative examples were measured according to the method set forthbelow. Here, “%” means “% by weight” unless otherwise noted. In thetable, the units for the cationic exchange abilities are each simplyexpressed as “mg/g.”

[0065] (1) Average Primary Particle Size

[0066] The primary particle size of zeolite particle for 100 or moreparticles is measured by a digitizer (commercially available fromGRAPHTEC CORPORATION, “DIGITIZER KW3300”), on the basis of the scanningelectron photomicrographs of a sample zeolite taken by a field-emissionhigh resolution scanning electron microscope (FE-SEM, commerciallyavailable from Hitachi Ltd., S-4000). The number-average value (averageprimary particle size) and the variation coefficient (%) are calculatedon the basis of the entire resulting determination values as population.Here, the variation coefficient is calculated by the following equation:$\begin{matrix}{Variation} \\{{Coefficient}\quad (\%)}\end{matrix} = {\frac{{Standard}\quad {Deviation}\quad ({µm})}{{Average}\quad {Primary}\quad {Particle}\quad {Size}\quad ({µm})} \times 100}$

[0067] (2) Powder X-ray Diffraction

[0068] The powder sample is subjected to powder X-ray diffraction atroom temperature (20° C.) by using a powder X-ray diffractometer,commercially available from Rigaku Denki, “RINT 2500 VPC” (light source:CuKα ray, tube voltage: 40 kV, and tube electric current: 120 mA) underthe conditions of a scanning interval of 0.01° in the range of 2θ=5° to40°, a scanning speed of 10°/minute, a divergence vertical limiting slitof 10 mm, a divergence slit of 1°, a light-intercepting slit of 0.3 mm,and a scattering slit being automatic. With taking background levelpoints at 2θ=20°, 28.5°, 37° and 40°, a background curve is drawn bythird-order polynomial, and a peak area A_(peak), an area formed betweenthe diffraction curve in the range of 2θ=20° to 40° and the backgroundcurve is determined. A_(r), which is a proportion of a peak area(A_(peak)) above the background level in all peak area (A_(all)) in therange of 2θ=20° to 40° is calculated from the peak area and all the peakarea as follows:${A_{r}\quad (\%)} = {\frac{A_{peak}}{A_{all}} \times 100}$

[0069] The term “all peak area” refers to an area formed between thediffraction curve in the range of 2θ=20° to 40° and a straight line ofintensity zero. In addition, the crystallinity degradation ratio bypulverization is calculated by the following equation: $\begin{matrix}\begin{matrix}{Crystallinity} \\{Degradation}\end{matrix} \\{{Ratio}\quad (\%)}\end{matrix} = {\frac{1 - \left( {A_{r}\quad {of}\quad {Zeolite}\quad {After}\quad {Pulverization}} \right)}{\left( {A_{r}\quad {of}\quad {Zeolite}\quad {Before}\quad {Pulverization}} \right)} \times 100}$

[0070] Further, the powder X-ray diffraction intensity ratio (%) iscalculated as a ratio of a powder X-ray diffraction peak intensity(I₄₁₀) having a face distance d=0.3 nm belonging to a face (I₄₁₀) ofA-type zeolite obtained for the zeolite to be analyzed to I₄₁₀ of acommercially available A-type zeolite (“TOYOBUILDER,” commerciallyavailable from TOSOH CORPORATION, I₄₁₀=32837 cps) having an averageprimary particle size of 1 μm or more.

[0071] (3) Average Aggregate Particle Size

[0072] The particle size distribution is measured with a slurry preparedby dispersing a sample in water as a dispersion medium under conditionsof a refractive index of 1.2, an ultrasonic intensity of 7, anultrasonication irradiation time of 1 minute, and a flow rate of 4,using a laser diffraction/scattering particle size distribution analyzer(commercially available from HORIBA Ltd., LA-920). The median diameter(calculated on the basis of volume) obtained is considered as an averageaggregate particle size (μm).

[0073] (4) Cationic Exchange Capacity

[0074] The amount 0.2 g of a water-based liquid of 20% zeolite is addedto 100 mL of an aqueous calcium chloride (100 ppm calcium concentration,calculated as CaCO₃), and stirred at 20° C. for 1 minute or 10 minutes,and the mixture is filtered with a disposable filter with 0.2 μm poresize. Thereafter, 10 mL of the resulting filtrate is taken and assayedfor a Ca content in the filtrate by using a photometric titrationapparatus, and cationic exchange abilities are determined. Incidentally,the Ca content (calculated as the amount of CaCO₃) ion-exchanged per 1 gof the zeolite in 1 minute is referred to as “cationic exchange rate(CER, expressed as mg CaCO₃/g)”, and the Ca content (calculated as theamount of CaCO₃) ion-exchanged per 1 g of the zeolite in 10 minutes isreferred to as “cationic exchange capacity (CEC, expressed as mgCaCO₃/g).”

[0075] (5) Turbidity

[0076] The turbidity (%) of a water-based liquid of zeolite (zeoliteconcentration: 0.013%) prepared by stirring the zeolite in water havingwater hardness of 4° at room temperature (20° C.) for 10 minutes isdetermined by using a turbidimeter commercially available from MurakamiColor Research Laboratory, reflectance-transmittance meter HR-100.

[0077] (6) Detergency

[0078] Forty grams of a crystalline silicate (KWS-2, particle size: 11μm, commercially available from Kao Corporation) is added to a mixedsolution of 24.8 g of a nonionic surfactant (EMULGEN 108, commerciallyavailable from Kao Corporation), 14.8 g of a polyoxyethylene phenylether (commercially available from Nippon Nyukazai) and 0.4 g of apolymer-type dispersant (AQUALOCK FC 600S, commercially available fromNIPPON SHOKUBAI CO., LTD.), and the resulting mixture is homogeneouslymixed with stirring. The resulting silicate-containing liquid mixture isplaced in a 1-L batch-type sand-mill (commercially available from IMEX)together with 500 g of zirconia beads (diameter: 1 mm), and subjected topulverization at a disc rotational speed of 1500 rpm for 60 minutes.Next, 0.3333 g of a liquid mixture containing the silicate after thepulverization (particle size: 2.3 μm) and 0.3333 g of a water-basedliquid of zeolite (zeolite concentration: 20%) are mixed, to give adetergent composition. Five pieces of artificially soiled cloths arewashed by washing with the resulting detergent composition for 10minutes, rinsing for 1 minute and drying using a turg-O-meter (120 rpm,commercially available from Ueshima Seisakusho) in 1 L of water havingwater hardness of 4° at a water temperature of 20° C., and the detergingrate (%) is determined. Here, the deterging rate is determined bymeasuring the reflectances at 550 nm of an unsoiled cloth and theartificially soiled cloth before and after washing by an automaticrecording calorimeter (commercially available from ShimadzuCorporation), and calculated by the following equation. $\begin{matrix}{Deterging} \\{{Rate}\quad (\%)}\end{matrix} = {\frac{\begin{matrix}\left\lbrack {{{Reflectance}\quad {After}\quad {Washing}} -} \right. \\\left. {{Reflectance}\quad {Before}\quad {Washing}} \right\rbrack\end{matrix}}{\begin{matrix}\left\lbrack {{{Reflectance}\quad {of}\quad {Unsoiled}\quad {Cloth}} -} \right. \\\left. {{Reflectance}\quad {Before}\quad {Washing}} \right\rbrack\end{matrix}} \times 100}$

[0079] The deterging rate is obtained as an average of 5 pieces ofcloths.

[0080] The artificially soiled cloths described above are prepared bysmearing a cloth (#2003 calico, commercially available from TanigashiraShoten) with an artificial soil solution having the followingcomposition. The smearing of the cloths with the artificial soilsolution is carried out using a gravure roll coater (cell capacity: 58cm, coating speed: 1 m/minute, drying temperature: 100° C., and dryingtime: 1 minute) made in accordance with Japanese Patent Laid-Open No.Hei 7-270395.

[0081] (Composition of Artificial Soil Solution)

[0082] The composition of the artificial soil solution is as follows:Lauric acid: 0.44%, myristic acid: 3.09%, pentadecanoic acid: 2.31%,palmitic acid: 6.18%, heptadecanoic acid: 0.44%, stearic acid: 1.57%,oleic acid: 7.75%, triolein: 13.06 /o, n-hexadecyl pahmitate: 2.18%,squalene: 6.53%, liquid crystalline product of lecithin, from egg yolk(commercially available from Wako Pure Chemical Industries): 1.94%,Kanuma red clay for gardening: 8.11%, carbon black (commerciallyavailable from Asahi Carbon.): 0.01%, and tap water: balance.

[0083] (7) Rinsing Performance

[0084] Using a detergent composition prepared by mixing a zeolite 22%, acrystalline silicate (SKS-6, particle size: 26 μm, commerciallyavailable from Clariant) 11%, and a nonionic surfactant (EMULGEN 108,commercially available from Kao Corporation) 67%, the clothes are washedfor 10 minutes under the conditions of a liquor ratio of 1/20, aconcentration of the detergent composition of 20 g/30 L, and a watertemperature of 20° C. in tap water having water hardness of 4°, and thenrinsed for 4 minutes at a rinsing flow rate of 15 L/minute, using atwin-tub washing machine commercially available from TOSHIBACORPORATION, “GINGA 3.6”. Thereafter, the transparency of the rinsing isvisually confirmed, and the rinsing performance is evaluated on thebasis of the following evaluation criteria. Specifically, after theclothes in the washtub are moved to the side wall of the washtub afterstopping the washing machine, the rinsing performance is evaluated onthe basis of the 3 grade-evaluation criteria:

[0085] ◯: the case where the rinsing is transparent, and the pulsator atthe bottom of the washtub is clearly seen;

[0086] Δ: the case where the rinsing is slightly turbid, but thepulsator can be seen; and

[0087] x: the case where the rinsing is turbid and the contour of thepulsator cannot be clearly seen.

EXAMPLE 1

[0088] (1) Preparation of Zeolite

[0089] Two-hundred grams of a nonionic surfactant (compound name:polyoxyethylene lauryl ether, EMULGEN 108, commercially available fromKao Corporation) was added to 400 g of an aqueous sodium aluminatesolution (Na₂O: 21.01%, Al₂O₃: 28.18%) contained in a 2 L-stainlesscontainer, while stirring with Teflon agitation blades each having alength of 11 cm at 400 rpm. The resulting mixture was heated at 50° C.for 20 minutes using a mantle heater. The amount 445 g of No. 3 waterglass (Na₂O: 9.68%, SiO₂: 29.83%, commercially available from OsakaKeiso) was added dropwise to the resulting solution over 5 minutes usinga roller pump. After the termination of the dropwise addition, themixture was further stirred for 10 minutes (400 rpm), and heated to 80°C. over 30 minutes while stirring. Thereafter, the mixture was furtheraged for 60 minutes. The resulting water-based liquid of fine zeoliteparticles was filtered, and washed with water until the filtrate had apH of less than 12. The filtrate was dried at 100° C. for 13 hours, andcrushed for 1 minute with a cooking cutter. The resulting powder wassubjected to powder X-ray diffraction measurement. As a result, it wasconfirmed that A-type zeolite (powder X-ray diffraction intensity ratio:46%) was formed. In addition, the average primary particle size of thezeolite particles was 0.03 μm.

[0090] (2) Pulverization of Zeolite

[0091] A water-based liquid of zeolite prepared by dispersing 10 g ofthe resulting powder of fine A-type zeolite particles in 40 g ofion-exchanged water was placed in a sealed container (capacity: 250 mL,made of polystyrene) together with 300 g of zirconia balls having adiameter of 5 mm, and pulverized with a ball-mill (300 rpm) for 24hours. The concentration of Al eluted in the filtrate, obtained byultrafiltering the water-based liquid of zeolite after the pulverization(zeolite concentration: 20%) with Ultrafilter Unit USY-1, molecularweight cut off: 10000, commercially available from ADVANTEC, wasquantified by ICP (Inductively coupled plasma spectrometry) analysis.The concentration of the total Al contained in the zeolite in thewater-based liquid of 20% zeolite was 3% of the liquid, and theconcentration of eluted Al obtained by the ICP analysis was 900 ppm. Theproportion of the amount of the eluted Al in the amount of the total Alwas found to be 3%. Incidentally, the proportion of the amount of elutedAl of the zeolite obtained in the above item (1) without pulverizationwas also determined in the same manner as above.

[0092] Also, various properties of the zeolite before and after thepulverization were determined in the manner as described above.Incidentally, the zeolite after the pulverization was evaluated usingthose obtained by drying the filtered precipitates, which were obtainedduring the determination of the amount of the eluted Al, at 100° C. for13 hours. In addition, the cationic exchange abilities, the turbidity,the deterging rate, and the rinsing performance were evaluated using thezeolite after the pulverization.

EXAMPLE 2

[0093] (1) Preparation of Zeolite

[0094] The amount 137 g of a polyethylene glycol (PEG 600, averagemolecular weight: 600, commercially available from Wako Pure ChemicalIndustries) was added to 400 g of an aqueous sodium aluminate solution(Na₂O: 21.01%, Al₂O₃: 28.18%) contained in a 2 L-stainless container,while stirring with Teflon agitation blades each having a length of 11cm at 400 rpm. The resulting mixture was heated at 50° C. for 20 minutesusing a mantle heater. The amount 445 g of No. 3 water glass (Na₂O:9.68%, SiO₂: 29.83%, commercially available from Osaka Keiso) was addeddropwise to the resulting solution over 5 minutes using a roller pump.After the termination of the dropwise addition, the mixture was furtherstirred for 10 minutes (400 rpm), and heated to 80° C. over 30 minutes,while stirring. Thereafter, the mixture was further aged for 60 minutes.The resulting water-based liquid of fine zeolite particles was filtered,and washed with water until the filtrate had a pH of less than 12. Thefiltrate was dried at 100° C. for 13 hours, and crushed for 1 minutewith a cooking cutter. The resulting powder was subjected to powderX-ray diffraction measurement. As a result, it was confirmed that A-typezeolite (powder X-ray diffraction intensity ratio: 48%) was formed. Inaddition, the average primary particle size of the zeolite particles was0.03 μm.

[0095] (2) Pulverization of Zeolite

[0096] A water-based liquid of zeolite prepared by dispersing 16 g ofthe resulting powder of fine A-type zeolite particles in 64 g ofion-exchanged water was placed in a pulverizing vessel made of Teflontogether with 500 g of zirconia beads having a diameter of 0.5 mm, and asand-mill pulverization was carried out at 1500 rpm for 20 minutes. Theconcentration of Al eluted in the filtrate, obtained by ultrafilteringthe water-based liquid of zeolite after the pulverization (zeoliteconcentration: 20%) with Ultrafilter Unit USY-1, molecular weight cutoff: 10000, commercially available from ADVANTEC, was quantified by ICPanalysis. The concentration of the total Al contained in the zeolite inthe water-based liquid of 20% zeolite was 3% of the liquid, and theconcentration of eluted Al obtained by the ICP analysis was 700 ppm. Theproportion of the amount of the eluted Al in the amount of the total Alwas found to be 2.3%. In addition, various properties of the zeolitewere determined in the same manner as in Example 1.

EXAMPLE 3

[0097] (1) Preparation of Zeolite

[0098] Two-hundred grams of a sodium aluminate powder (Na₂O: 40.1%,Al₂O₃: 53.8%, NAP-120, commercially available from Sumitomo ChemicalCompany, Limited) was added to 147 g of a 40% aqueous acrylate polymersolution (Oligomer D, weight-average molecular weight: 10000,commercially available from Kao Corporation) contained in a 2L-stainless container, while stirring with Teflon agitation blades eachhaving a length of 11 cm at 400 rpm. The resulting mixture was heated at50° C. for 20 minutes using a mantle heater. The amount 428 g of No. 3water glass (Na₂O: 9.68%, SiO₂: 29.83%, commercially available fromOsaka Keiso) was added dropwise to the resulting solution over 5 minutesusing a roller pump. After the termination of the dropwise addition, themixture was further stirred for 10 minutes (400 rpm), and heated to 80°C. over 30 minutes while stirring. Thereafter, the mixture was furtheraged for 60 minutes. The resulting water-based liquid of fine zeoliteparticles was filtered, and washed with water until the filtrate had apH of less than 12. The filtrate was dried at 100° C. for 13 hours, andcrushed for 1 minute with a cooking cutter. The resulting powder wassubjected to powder X-ray diffraction measurement. As a result, it wasconfirmed that A-type zeolite (powder X-ray diffraction intensity ratio:49%) was formed. In addition, the average primary particle size of thezeolite particles was 0.03 μm.

[0099] (2) Pulverization of Zeolite

[0100] A water-based liquid of zeolite prepared by dispersing 10 g ofthe resulting powder of fine A-type zeolite particles in 40 g ofion-exchanged water was placed in a sealed container (capacity: 250 mL,made of polystyrene) together with 300 g of zirconia balls having adiameter of 5 mm, and a ball-mill pulverization was carried out at 300rpm for 24 hours. The concentration of Al eluted in the filtrateobtained by ultrafiltering the water-based liquid of zeolite after thepulverization (zeolite concentration: 20%) with Ultrafilter Unit USY-1,molecular weight cut off: 10000, commercially available from ADVANTEC,was quantified by ICP analysis. The concentration of the total Alcontained in the zeolite in the water-based liquid of 20% zeolite was 3%of the liquid, and the concentration of eluted Al obtained by the ICPanalysis was 700 ppm. The proportion of the amount of the eluted Al inthe amount of the total Al was found to be 2.3%. In addition, variousproperties of the zeolite were determined in the same manner as inExample 1.

COMPARATIVE EXAMPLE 1

[0101] (1) Preparation of Zeolite

[0102] The amount 211 g of an aqueous sodium hydroxide (48% aqueousNaOH) was added to 400 g of an aqueous sodium aluminate solution (Na₂O:21.01%, Al₂O₃: 28.18%) contained in a 2 L-stainless container, whilestirring with Teflon agitation blades each having a length of 11 cm at400 rpm. The resulting mixture was heated at 50° C. for 20 minutes usinga mantle heater. A mixed solution of 445 g of No. 3 water glass (Na₂O:9.68%, SiO₂: 29.83%, commercially available from Osaka Keiso) and 236 gof an aqueous calcium chloride (1% aqueous CaCl₂) was added dropwise tothe resulting solution over 5 minutes using a roller pump. After thetermination of the dropwise addition, the mixture was further stirredfor 10 minutes (400 rpm), and heated to 80° C. over 30 minutes whilestirring. Thereafter, the mixture was further aged for 5 minutes. Theresulting water-based liquid of zeolite was filtered, and washed withwater until the filtrate had a pH of less than 12. The filtrate wasdried at 100° C. for 13 hours, and crushed for 1 minute with a cookingcutter. The resulting powder was subjected to powder X-ray diffractionmeasurement. As a result, it was confirmed that A-type zeolite (powderX-ray diffraction intensity ratio: 62%) was formed. In addition, theaverage primary particle size of the zeolite particles was 0.2 μm.

[0103] (2) Pulverization of Zeolite

[0104] The zeolite was pulverized, and the concentration of Al elutedtherefrom was quantified by ICP analysis, in the same manner as inExample 1. The concentration of the total Al contained in the zeolite inthe water-based liquid of 20% zeolite was 3% of the liquid, and theconcentration of eluted Al obtained by the ICP analysis was 1300 ppm.The proportion of the amount of the eluted Al in the amount of the totalAl was found to be 4.3%. In addition, various properties of the zeolitewere determined in the same manner as in Example 1.

COMPARATIVE EXAMPLE 2

[0105] Various properties of the zeolite were determined in the samemanner as in Example 1 using a commercially available A-type zeolite(TOYOBUILDER, commercially available from Tosoh Corporation), exceptthat zeolite was not pulverized in this Comparative Example.

COMPARATIVE EXAMPLE 3

[0106] Various properties of the zeolite were determined in the samemanner as in Example 1 using a commercially available 4A zeolite(TOYOBUILDER, commercially available from Tosoh Corporation). Here, theconcentration of the total Al contained in the zeolite in thewater-based liquid of 20% zeolite was 3% of the liquid, and theconcentration of eluted Al obtained by ICP analysis after thepulverization was 1200 ppm. The proportion of the amount of the elutedAl in the amount of the total Al was found to be 4%.

COMPARATIVE EXAMPLE 4

[0107] The amount 155 g of propylene glycol (molecular weight: 76,commercially available from Wako Pure Chemical Industries) was added to400 g of an aqueous sodium aluminate solution (Na₂O: 21.01%, Al₂O₃:28.18%) contained in a 2 L-stainless container, while stirring withTeflon agitation blades each having a length of 11 cm at 400 rpm. Theresulting mixture was heated at 50° C. for 20 minutes using a mantleheater. The amount 445 g of No. 3 water glass (Na₂O: 9.68%, SiO₂:29.83%, commercially available from Osaka Keiso) was added dropwise tothe resulting solution over 5 minutes using a roller pump. After thetermination of the dropwise addition, the mixture was further stirredfor 10 minutes (400 rpm), and heated to 80° C. over 30 minutes whilestirring. Thereafter, the mixture was further aged for 60 minutes. Theresulting water-based liquid of fine zeolite particles was filtered, andwashed with water until the filtrate had a pH of less than 12. Thefiltrate was dried at 100° C. for 13 hours, and crushed for 1 minutewith a cooking cutter. The resulting powder was subjected to powderX-ray diffraction measurement. As a result, it was confirmed that A-typezeolite (powder X-ray diffraction intensity ratio: 61%) was formed. Inaddition, the average primary particle size of the zeolite particles was0.2 μm. The zeolite was pulverized, and evaluated in the same manner asin Example 1. The concentration of the total Al in the water-basedliquid of 20% zeolite was 3% of the liquid, and the concentration ofeluted Al obtained by the ICP analysis was 1300 ppm. The proportion ofthe amount of the eluted Al in the amount of the total Al was found tobe 4.3%. In addition, various properties of the zeolite were determinedin the same manner as in Example 1.

[0108] The feeding composition of zeolite is shown in Table 1, and theresults described above are summarized in Table 2. TABLE 1 ExamplesComparative Examples 1 2 3 1 2 3 4 Feeding Composition Molar RatioSiO₂/Al₂O₃ 2.0 2.0 2.0 2.0 — — 2.0 Na₂O/Al₂O₃ 1.9 1.9 1.9 3.0 — — 1.9CaO/Al₂O₃ 0 0 0 0.02 — — 0 Na₂O/H₂O 0.078 0.078 0.078 0.065 — — 0.078Al₂O₃/H₂O 0.042 0.042 0.042 0.022 — — 0.042 Crystallization Inhibitor 1914 6.8 0 0 0 15 (%) Solid Content (%) 36 38 41 35 — — 37 ProductComposition Molar Ratio SiO₂/Al₂O₃ 2.0 2.0 2.0 2.0 2.0 2.0 2.0Na₂O/Al₂O₃ 1.1 1.1 1.0 1.1 1.1 1.1 1.1 CaO/Al₂O₃ 0 0 0 0.02 0 0 0Crystal Form A-Type A-Type A-Type A-Type A-Type A-Type A-Type

[0109] TABLE 2 Comparative Examples 1 2 3 4 Examples Commercially 1 2 3Commercially Available Prepared and Prepared and Prepared and Preparedand Available Product, Prepared and Zeolite Pulverized PulverizedPulverized Pulverized Product Pulverized Pulverized CrystallizationInhibitor Nonionic Polyethylene Acrylate — — — Propylene (MolecularWeight) Surfactant Glycol Polymer Glycol (454) (600) (10000) (76)Average Primary Particle Size ([82 m) [Variation Coefficient] (%) BeforePulverization 0.03 0.03 0.03 0.2 1.8 1.8 0.2 [16] [23] [14] [30] [30][30] [30] After Pulverization 0.03 0.03 0.03 0.03 — 0.04 0.03 [20] [25][20] [18] [100] [20] Average Aggregate Particle Size ([82 m) BeforePulverization 15 17 9.9 3.2 4.0 4.0 16 After Pulverization 0.37 0.330.40 0.38 — 0.48 0.40 A_(r) (%) Before Pulverization 53.4 52.7 50.4 61.066.2 66.2 60.6 After Pulverization 35.1 42.3 34.0 27.2 — 43.3 27.4Crystallinity Degradation Ratio (%) 34.3 19.7 32.5 55.4 — 34.6 54.8Amount of Eluted Al (%) Before Pulverization 0.7 0.2 0.3 0.2 0.1 0.1 0.2After Pulverization 3.0 2.3 2.3 4.3 — 4.0 4.3 Powder X-Ray DiffractionIntensity Ratio (%) Before Pulverization 46 48 49 62 100 100 61 AfterPulverization 28 28 30 24 — 47 25 Cationic Exchange Rate (mg/g) 220 220220 210 160 210 210 Cationic Exchange Capacity (mg/g) 220 220 220 220220 220 220 Turbidity (%) 17 25 29 24 50 32 30 Detergent CompositionDeterging Rate (%) 60 60 60 45 50 47 45 Rinsing Performance ◯ ◯ ◯ ◯ X ΔΔ

[0110] It is clear from Examples 1 to 3 that there can be obtained fineA-type zeolite particles having an average primary particle size of 0.1μm or less by carrying out the reaction of preparing zeolite in thepresence of crystallization inhibitor according to the process forpreparing fine zeolite particles of the present invention. InComparative Example 4 where the reaction of preparing zeolite is carriedout in the presence of a propylene glycol, which is an organic compoundhaving an oxygen-containing functional group, the molecular weight ofthe compound is 76, so that fume zeolite particles having an averageprimary particle size of 0.1 μm or less are not obtained.

[0111] In addition, the average aggregate particle size of the zeoliteparticles of Examples and Comparative Examples can be adjusted to 0.4 μmor less by an appropriate pulverization. However, in the zeoliteparticles of Comparative Examples 1, 3 and 4, of which average primaryparticle size before pulverization is more than 0.1 μm after thepulverization, the crystallinity degradation progresses, thedeterioration of the average primary particle size distribution isobserved, and the amount of the eluted Al is increased. Therefore, it isseen that the deterging rate and/or the rinsing performance of thedetergent compositions obtained using the zeolite is lowered. On theother hand, in Examples 1 to 3, the progress of the crystallinitydegradation (for example, crystallinity degradation ratio) issuppressed, and the average primary particle size distribution is notsubstantially changed, even when the zeolite is pulverized. Therefore,in these Examples, there are obtained fine zeolite particles which havea desired average aggregate particle size and excellent cationicexchange abilities, so that it is seen that the deterging rate and therinsing performance of the detergent compositions obtained by using thezeolite are high.

INDUSTRIAL APPLICABILITY

[0112] According to the present invention, there can be obtained finezeolite particles having an average primary particle size of 0.1 μm orless and excellent cationic exchange abilities, with a small amount ofAl eluted in water in a water-based liquid as well as a low turbidity ofwater of the liquid. In addition, there can be obtained a detergentcomposition comprising the fine zeolite particles, which is highlyexcellent in the detergency and rinsing performance. The fine zeoliteparticle of the present invention is suitably used for detergentbuilders, water treatment agents, fillers for paper, resin fillers,oxygen-nitrogen separating agents, adsorbents, catalyst carriers, soilimprovers for gardening, polishing agents, and the like.

1. A fine A-type zeolite particle having an average primary particlesize of 0.1 μm or less and a variation coefficient of 90% or less,wherein a ratio of a peak area above a background level to all peak areain the range of 2θ=20° to 40° in a powder X-ray diffraction spectrum ofsaid fine A-type zeolite particle is 30% or more.
 2. The fine A-typezeolite particle according to claim 1, wherein the fine A-type zeoliteparticle has an average aggregate particle size of 0.4 μm or less. 3.The fine A-type zeolite particle according to claim 1 or 2, wherein whenwater-based liquid of the particle is prepared, a ratio of the amount ofAl eluted in water is less than 4% by weight of all the amount of Alcontained in the zeolite.
 4. The fine A-type zeolite particle accordingto claim 1, wherein the fine A-type zeolite particle has a cationicexchange rate is 180 mg CaCO₃/g or more.
 5. A process for preparing thefine A-type zeolite particle of claim 1, comprising reacting a silicasource with an aluminum source in the presence of an organic compoundhaving an oxygen-containing functional group and a molecular weight of100 or more.
 6. The process according to claim 5, wherein theoxygen-containing functional group is at least one of OR group and COORgroup, wherein R is at least one member selected from a saturated orunsaturated organic group having 1 to 22 carbon atoms, hydrogen atom andan alkali metal atom.
 7. A detergent composition comprising a surfactantand the fine A-type zeolite particle of claim 1.